Fungicidal mixtures based on amide compounds and morpholine or piperidine derivatives

ABSTRACT

Fungicidal mixtures comprise as active components
         a) an amide compound of the formula I
 
A-CO—NR 1 R 2   I
 
in which A, R 1  and R 2  are as defined in the description, and
   b) dimethomorph or flumetover, and/or   c) a valinamide of the formula III       

     
       
         
         
             
             
         
       
         
         
           
             
               
                 in which 
                 R 13  is C 3 -C 4 -alkyl and 
                 R 14  is naphthyl or phenyl, where the phenyl radical is substituted in the 4-position by a halogen atom, a C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy group, and/or 
               
             
             d) benalaxyl, ofurace, metalaxyl, furalaxyl or oxydixyl, and/or 
             e) 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea 
             in a synergistically effective amount.

This is a Divisional application of application Ser. No. 10/183,618,filed on Jun. 28, 2002 (allowed), the entire disclosure of which isherewith incorporated by reference, which is a Divisional application ofapplication Ser. No. 09/581,834, filed on Jun. 19, 2000, now U.S. Pat.No. 6,436,934, the entire disclosure of which is herewith incorporatedby reference.

The present invention relates to fungicidal mixtures for controllingharmful fungi and also to methods for controlling harmful fungi usingsuch mixtures.

WO 97/08952 describes mixtures of amide compounds of the formula IA-CO—NR¹R²  (I)in which

-   A is an aryl group or an aromatic or non-aromatic, 5- or 6-membered    heterocycle which has from 1 to 3 heteroatoms selected from O, N and    S;    -   where the aryl group or the heterocycle may or may not have 1, 2        or 3 substituents which are selected, independently of one        another, from alkyl, halogen, CHF₂, CF₃, alkoxy, haloalkoxy,        alkylthio, alkylsulfynyl and alkylsulfonyl;-   R¹ is a hydrogen atom;-   R² is a phenyl or cycloalkyl group which may or may not have 1, 2 or    3 substituents which are selected from alkyl, alkenyl, alkynyl,    alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl,    cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, where the    aliphatic and cycloaliphatic radicals may be partially or fully    halogenated and/or the cycloaliphatic radicals may be substituted by    from 1 to 3 alkyl groups and where the phenyl group may have from 1    to 5 halogen atoms and/or from 1 to 3 substituents which are    selected, independently of one another, from alkyl, haloalkyl,    alkoxy, haloalkoxy, alkylthio and haloalkylthio, and where the    amidic phenyl group may or may not be condensed with a saturated    5-membered ring which may or may not be substituted by one or more    alkyl groups and/or may have a heteroatom selected from O and S, and    the active ingredient fenazaquin which is known as an acaricide.

These mixtures are described as being particularly effective againstBotrytis.

It is an object of the present invention to provide further particularlyeffective mixtures for controlling harmful fungi and in particular forcertain indications.

We have found, surprisingly, that this object is achieved by a mixturewhich comprises as active ingredients amide compounds of the formula Idefined above and as further fungicidally active component

-   -   b) a carboxamide II selected from the group of the compounds IIa        and IIb

and/or

-   -   c) a valinamide of the formula III

in which

-   R¹³ is C₃-C₄-alkyl and-   R¹⁴ is naphthyl or phenyl, where the phenyl radical in the    4-position is substituted by a halogen atom, a C₁-C₄-alkyl or a    C₁-C₄-alkoxy group,    and/or    -   d) at least one active ingredient of the formulae IV.1 to IV.5,

and/or

-   -   e) 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (V)        H₃CCH₂—NHCONH—C(CN)═NOCH₃  V        in a synergistically effective amount.

The mixtures according to the invention have synergistic action and aretherefore particularly suitable for controlling harmful fungi and inparticular downy mildew fungi in vegetables and grapevines.

In the context of the present invention, halogen is fluorine, chlorine,bromine and iodine and is in particular fluorine, chlorine and bromine.

The term “alkyl” includes straight-chain and branched alkyl groups.These are preferably straight-chain or branched C₁-C₁₂-alkyl and inparticular C₁-C₆-alkyl groups. Examples of alkyl groups are alkyl suchas, in particular, methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl,1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl,2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl,1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl.

Haloalkyl is an alkyl group as defined above which is partially or fullyhalogenated by one or more halogen atoms, in particular by fluorine andchlorine. Preferably, there are from 1 to 3 halogen atoms present, andthe difluoromethyl or the trifluoromethyl group is particularlypreferred.

The above statements for the alkyl group and the haloalkyl group applyin a corresponding manner to the alkyl and haloalkyl groups in alkoxy,haloalkoxy, alkylthio, haloalkylthio, alkylsulfynyl and alkylsulfonyl.

The alkenyl group includes straight-chain and branched alkenyl groups.These are preferably straight-chain or branched C₃-C₁₂-alkenyl groupsand in particular C₃-C₆-alkenyl groups. Examples of alkenyl groups are2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl,2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and1-ethyl-2-methyl-2-propenyl, in particular 2-propenyl, 2-butenyl,3-methyl-2-butenyl and 3-methyl-2-pentenyl.

The alkenyl group may be partially or fully halogenated by one or morehalogen atoms, in particular by fluorine or chlorine. This grouppreferably has from 1 to 3 halogen atoms.

The alkynyl group includes straight-chain and branched alkynyl groups.These are preferably straight-chain and branched C₃-C₁₂-alkynyl groupsand in particular C₃-C₆-alkynyl groups. Examples of alkynyl groups are2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl,1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl,2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl,1,2-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl.

The above statements for the alkenyl group and its halogen substituentsand for the alkynyl group apply in a corresponding manner to alkenyloxyand alkynyloxy.

The cycloalkyl group is preferably a C₃-C₆-cycloalkyl group, such ascyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

If the cycloalkyl group is substituted, it preferably has from 1 to 3C₁-C₄-alkyl radicals as substituents.

Cycloalkenyl is preferably a C₄-C₆-cycloalkenyl group, such ascyclobutenyl, cyclopentenyl or cyclohexenyl. If the cycloalkenyl groupis substituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicals assubstituents.

A cycloalkoxy group is preferably a C₅-C₆-cycloalkoxy group, such ascyclopentyloxy or cyclohexyloxy. If the cycloalkoxy group issubstituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicals assubstituents.

The cycloalkenyloxy group is preferably a C₅-C₆-cycloalkenyloxy group,such as cyclopentyloxy or cyclohexyloxy. If the cycloalkenyloxy group issubstituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicals assubstituents.

Aryl is preferably phenyl.

If A is a phenyl group, this may have one, two or three of theabovementioned substituents in any position. These substituents arepreferably selected, independently of one another, from alkyl,difluoromethyl, trifluoromethyl and halogen, in particular chlorine,bromine and iodine. Particularly preferably, the phenyl group has asubstituent in the 2-position.

If A is a 5-membered heterocycle, it is in particular a furyl,thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, triazolyl orthiadiazolyl radical or the corresponding dihydro or tetrahydroderivatives thereof. Preference is given to a thiazolyl or pyrazolylradical.

If A is a 6-membered heterocycle, it is in particular a pyridyl radicalor a radical of the formula:

in which one of the radicals X and Y is O, S or NR¹², where R¹² is H oralkyl, and the other of the radicals X and Y is CH₂, S, SO, SO₂ or NR¹².The dotted line means that a double bond may or may not be present.

The 6-membered aromatic heterocycle is particularly preferably a pyridylradical, in particular a 3-pyridyl radical, or a radical of the formula

in which X is CH₂, S, SO or SO₂.

The abovementioned heterocyclic radicals may or may not have 1, 2 or 3of the abovementioned substituents, where these substituents arepreferably selected, independently of one another, from alkyl, halogen,difluoromethyl or trifluoromethyl.

A is particularly preferably a radical of the formulae:

in which R³, R⁴, R⁶, R⁷, R⁸ and R⁹ independently of one another arehydrogen, alkyl, in particular methyl, halogen, in particular chlorine,CHF₂ or CF₃.

The radical R¹ in the formula I is preferably a hydrogen atom.

The radical R² in the formula I is preferably a phenyl radical. R²preferably has at least one substituent which is particularly preferablyin the 2-position. The substituent (or the substituents) is (are)preferably selected from the group consisting of alkyl, cycloalkyl,cycloalkenyl, halogen and phenyl.

The substituents of the radical R² may in turn be substituted again. Thealiphatic or cycloaliphatic substituents may be partially or fullyhalogenated, in particular fluorinated or chlorinated. They preferablyhave 1, 2 or 3 fluorine or chlorine atoms. If the substituent of theradical R² is a phenyl group, this group may preferably be substitutedby from 1 to 3 halogen atoms, in particular chlorine atoms, and/or by aradical which is preferably selected from alkyl and alkoxy. Particularlypreferably, the phenyl group is substituted with a halogen atom in thep-position, i.e. the particularly preferred substituent of the radicalR² is a p-halogen-substituted phenyl radical. The radical R² may also becondensed with a saturated 5-membered ring, where this ring for its partmay have from 1 to 3 alkyl substituents.

R² is in this case, for example, indanyl, thiaindanyl and oxaindanyl.Preference is given to indanyl and 2-oxaindanyl which are attached tothe nitrogen atom in particular via the 4-position.

According to a preferred embodiment, the composition according to theinvention comprises as amide compound a compound of the formula I inwhich A is as defined below: phenyl, pyridyl, dihydropyranyl,dihydrooxathiynyl, dihydrooxathiynyloxide, dihydrooxathiynyldioxide,furyl, thiazolyl, pyrazolyl or oxazolyl, where these groups may have 1,2 or 3 substituents which are selected, independently of one another,from alkyl, halogen, difluoromethyl and trifluoromethyl.

According to a further preferred embodiment, A is: pyridin-3-yl, whichmay or may not be substituted in the 2-position by halogen, methyl,difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfynyl ormethylsulfonyl;

phenyl, which may or may not be substituted in the 2-position by methyl,trifluoromethyl, chlorine, bromine or iodine;

2-methyl-5,6-dihydropyran-3-yl;

2-methyl-5,6-dihydro-1,4-oxathiyn-3-yl or the 4-oxide or 4,4-dioxidethereof;

2-methylfuran-3-yl, which may or may not be substituted in the 4- and/or5-position by methyl;

thiazol-5-yl, which may or may not be substituted in the 2- and/or4-position by methyl, chlorine, difluoromethyl or trifluoromethyl;

thiazol-4-yl, which may or may not be substituted in the 2- and/or5-position by methyl, chlorine, difluoromethyl or trifluoromethyl;

1-methylpyrazol-4-yl, which may or may not be substituted in the 3-and/or 5-position by methyl, chlorine, difluoromethyl ortrifluoromethyl; or

oxazol-5-yl, which may or may not be substituted in the 2- and/or4-position by methyl or chlorine.

According to a further preferred embodiment, the compositions accordingto the invention comprise as amide compound a compound of the formula Iin which R² is a phenyl group which may or may not be substituted by 1,2 or 3 of the abovementioned substituents.

According to a further preferred embodiment, the compositions accordingto the invention comprise as amide compound a compound of the formula Iin which R² is a phenyl group which has one of the followingsubstituents in the 2-position:

C₃-C₆-alkyl, C₅-C₆-cycloalkenyl, C₅-C₆-cycloalkyloxy, cycloalkenyloxy,where these groups may be substituted by 1, 2 or 3 C₁-C₄-alkyl groups,

phenyl, which is substituted by from 1 to 5 halogen atoms and/or from 1to 3 groups which are selected, independently of one another, fromC₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio and C₁-C₄-haloalkylthio,

indanyl or oxaindanyl which may or may not be substituted by 1, 2 or 3C₁-C₄-alkyl groups.

According to a further preferred embodiment, the compositions accordingto the invention comprise as amide compound a compound of the formulaIa,

in whichA is

X is methylene, sulfur, sulfynyl or sulfonyl (SO₂),R³ is methyl, difluoromethyl, trifluoromethyl, chlorine, bromine oriodine,R⁴ is trifluoromethyl or chlorine,R⁵ is hydrogen or methyl,R⁶ is methyl, difluoromethyl, trifluoromethyl or chlorine,R⁷ is hydrogen, methyl or chlorine,R⁸ is methyl, difluoromethyl or trifluoromethyl,R⁹ is hydrogen, methyl, difluoromethyl, trifluoromethyl or chlorine,R¹⁰ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or halogen.

According to a particularly preferred embodiment, the compositionscomprise as amide compound a compound of the formula Ib

in whichR⁴ is halogen andR¹¹ is phenyl which is substituted by halogen.

Particularly preferred mixtures according to the invention comprise ascomponent I compounds of the formulae

Useful amide compounds of the formula I are mentioned in EP-A-545 099and 589 301 which are incorporated herein in their entirety byreference.

The preparation of the amide compounds of the formula I is known, forexample, from EP-A-545 099 or 589 301 or can be carried out by similarprocesses.

Also known are the carboxamides II [IIa: common name: dimethomorph, EP-A120 321; IIb: proposed common name: flumetover, AGROW No. 243, 22(1995)], their preparation and their action against harmful fungi.

The compounds of the formula III are also known per se. A firstpreferred group of valinamide derivatives are compounds of the formulaIII′

in which R¹³ is as defined above and X is halogen, C₁-C₄-alkyl orC₁-C₄-alkoxy. Compounds of this type and their preparation aredescribed, for example, in EP-A-0 610 764 and EP-A-0 398 072, which areexpressly incorporated herein by way of reference.

A further preferred group of valinamide derivatives are compounds of theformula III″

in which R¹³ is as defined above. Compounds of this type and theirpreparation are described, for example, in DE-A-43 21 897 andWO-A-96/07638, which are expressly incorporated herein by way ofreference.

Preference is given to compounds of the formula III in which R¹³ isisopropyl, sec-butyl and tert-butyl.

Likewise, preference is given to compounds of the formula III in whichR¹⁴ is a-naphthyl, β-naphthyl and phenyl, the phenyl radical beingsubstituted in the 4-position by chlorine, bromine, C₁-C₄-alkyl orC₁-C₄-alkoxy.

Particular preference is given to compounds of the formula III in whichR¹⁴ is SS-naphthyl, 4-chlorophenyl, 4-methylphenyl and 4-methoxyphenyl.

Preferred examples of valinamides which can be used according to theinvention are summarized in Table 2 below.

TABLE 2 No. R¹³ R¹⁴ III.1 isopropyl β-naphthyl III.2 isopropyl4-chlorophenyl III.3 isopropyl 4-methylphenyl III.4 isopropyl4-methoxyphenyl III.5 sec-butyl β-naphthyl III.6 sec-butyl4-chlorophenyl III.7 sec-butyl 4-methylphenyl III.8 sec-butyl4-methoxyphenyl III.9 tert-butyl β-naphthyl III.10 tert-butyl4-chlorophenyl III.11 tert-butyl 4-methylphenyl III.12 tert-butyl4-methoxyphenyl

Particular preference is given to the compounds 111.2 and III.9.

From the structural formula for the compounds of the formula III it isevident that these compounds have two asymmetrically substituted carbonatoms. The compounds can therefore be used for the mixture according tothe invention either as mixtures of different isomers or as pureisomers.

In a further preferred embodiment, compounds of the formula III are usedin which the amino acid moiety is formed by alkoxycarbonyl-L-valine (Sconfiguration) and the phenethylamine moiety or the naphthylethylaminemoiety has the R configuration. Such compounds can be represented by theformula IIIa

in which R¹³ and R¹⁴ are as defined for the compounds of the formula II.

The preparation of the preferred isomers of the formula IIIa is carriedout similarly to the methods described in the earlier German patentapplication DE-A-195 31 814. The disclosure of this application isexpressly incorporated herein by way of reference.

The isomerically pure compounds of the formula IIIa can be prepared in amanner known per se starting from the appropriate, L-valine-basedcarbamoylcarboxylic acids VI. The compounds IIIa are obtained, forexample, by the process described below in which a carbamoylcarboxylicacid VI is reacted with an amine VII (the literature references“Houben-Weyl” refer to: Houben-Weyl, Methoden der Organischen Chemie,4th edition, Thieme Verlag, Stuttgart):

The carbamoylcarboxylic acids VI are known or can be prepared by knownmethods, in particular starting from the amino acid L-valine (cf.“Houben-Weyl”, volume 15/1, pp. 46-305, in particular pp. 117-125).

The amines VII are also known or can be easily obtained (cf. Organikum,VEB Deutscher Verlag der Wissenschaften, 15th edition, Berlin, 1977, p.610 ff.; “Houben-Weyl”, volume 15/1, pp. 648-665; Indian J. Chem. 10,pp. 366 (1972); J. Am. Chem. Soc. 58, pp. 1808-1811 (1936)).

From racemates of the amines VII, the R isomer can be isolated in amanner known per se, for example by fractional crystallization usingoptically active tartaric acid or, preferably, by enzyme-catalyzedesterification and subsequent hydrolysis (cf., for example,WO-A-95/08636).

This process is preferably carried out by initially converting thecarbamoylcarboxylic acids VI into carboxyl-ativaited derivatives, inparticular into acyl cyanides or anhydrides, (cf. Tetrahedron Letters,volume 18, pp. 1595-1598 (1973), or “Houben-Weyl”, volume 15/1, pp.28-32). These derivatives are then reacted with the amines VII in thepresence of bases.

Suitable for preparing the carboxyl-activated acyl cyanides is, forexample, the reaction of the carbamoylcarboxylic acids V with diethylcyanophosphonate, in particular in an inert solvent, such astetrahydrofuran or toluene.

The preparation of the carboxyl-activated anhydrides is preferablycarried out by reacting the carbamoylcarboxylic acid V withchloroformates, such as isobutyl chloroformate, in the presence of basesand, if appropriate, in an inert solvent, such as toluene ortetrahydrofuran.

The reaction of the amines VII with the carboxyl-activatedcarbamoylcarboxylic acids VI is preferably carried out in a solvent suchas dichloromethane, tetrahydrofuran or toluene.

The amines VII may also serve as bases, in which case they are usuallyrecovered from the crude product.

In a preferred embodiment of this process step, the carbamoylcarboxylicacid VI, the amine VII, the reagent which is suitable for generating thecarboxyl-activated derivative of the carbamoylcarboxylic acid VI and thebase are reacted in a one-pot process, if appropriate in an inertsolvent, and the crude product is subsequently worked-up in a mannerknown per se to isolate the carbamoylcarboxamide IIIa.

The compound IV.1 is commercially available under the common namebenalaxyl or the trade name Galben™

The compound IV.2 is commercially available under the common nameofurace or the trade name Celtan™ P in the form of mixtures withcymoxanil and folpet.

The compound IV.3 is commercially available under the common namemetalaxyl or the trade name Ridomil™

The compound IV.4 is commercially available under the common namefuralaxyl or the trade name Fongaride™

The compound of the formula IV.5 is commercially available under thecommon name oxadixyl and under the trade name Sandofan™C in mixtureswith copper salts.

Processes for preparing the compounds of the formula IV are known per seto the person skilled in the art, and there is therefore no need tomention them here in any detail.

The compound V (U.S. Pat. No. 3,957,847; common name: cymoxanil), itspreparation and its action against harmful fungi are also known.

To unfold the synergistic activity, even a small amount of amidecompound of the formula I is sufficient. Preference is given toemploying amide compound and compounds II and/or the compounds III to Vin a weight ratio in the range of from 20:1 to 1:20, in particular 10:1to 1:10.

When preparing the mixtures, it is preferred to employ the pure activeingredients I and II and/or III to V, to which further activeingredients against harmful fungi or other pests, such as insects,arachnids or nematodes, or else herbicidal or growth-regulating activeingredients or fertilizers can be admixed.

The mixtures of the compounds I and II and/or III to V, or the compoundsI and II and/or III to V used simultaneously, jointly or separately,exhibit outstanding activity against a wide range of phytopathogenicfungi, in particular from the classes of the Ascomycetes,Basidiomycetes, Phycomycetes and Deuteromycetes. Some of them actsystemically and can therefore also be employed as foliar- andsoil-acting fungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants, such as cotton, vegetable species (eg.cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass,oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine,wheat, ornamentals, sugar cane, and a variety of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,Podosphaera leucotricha in apples, Uncinula necator in grapevines,Puccinia species in cereals, Rhizoctonia species in cotton, rice andlawns, Ustilago species in cereals and sugar cane, Venturia inaequalis(scab) in apples, Helminthosporium species in cereals, Septoria nodorumin wheat, Botrytis cinerea (gray mold) in strawberries, vegetables,ornamentals and grapevines, Cercospora arachidicola in groundnuts,Pseudocercosporella herpotrichoides in wheat and barley, Pyriculariaoryzae in rice, Phytophthora infestans in potatoes and tomatoes,Plasmopara viticola in grapevines, Pseudoperonospora species in hops andcucumbers, Alternaria species in vegetables and fruit, Mycosphaerellaspecies in bananas and Fusarium and Verticillium species.

The mixtures according to the invention may particularly preferably beemployed for controlling powdery mildew fungi in vegetables andgrapevines.

The compounds I and II and/or III to V can be applied simultaneously,either together or separately, or in succession, the sequence, in thecase of separate application, generally not having any effect on theresult of the control measures.

Depending on the kind of effect desired, the application rates of themixtures according to the invention are, in particular in agriculturalcrop areas, from 0.01 to 8 kg/ha, preferably from 0.1 to 5 kg/ha, inparticular from 0.5 to 3.0 kg/ha.

The application rates of the compounds I are from 0.01 to 2.5 kg/ha,preferably from 0.05 to 2.5 kg/ha, in particular from 0.1 to 1.0 kg/ha.

Correspondingly, in the case of the compounds II and/or III to V, theapplication rates are from 0.01 to 10 kg/ha, preferably from 0.05 to 5kg/ha, in particular from 0.05 to 2.0 kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 250 g/kg of seed, preferably from 0.01 to 100 g/kg, inparticular from 0.01 to 50 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate orjoint application of the compounds I and II and/or III to V or of themixtures of the compounds I and II and/or III to V is effected byspraying or dusting the seeds, the plants or the soils before or aftersowing of the plants, or before or after plant emergence.

The fungicidal synergistic mixtures according to the invention, or thecompounds I and II and/or III to V, can be formulated for example in theform of ready-to-spray solutions, powders and suspensions or in the formof highly concentrated aqueous, oily or other suspensions, dispersions,emulsions, oil dispersions, pastes, dusts, materials for broadcasting orgranules, and applied by spraying, atomizing, dusting, broadcasting orwatering. The use form depends on the intended purpose; in any case, itshould ensure as fine and uniform as possible a distribution of themixture according to the invention.

The formulations are prepared in a known manner, eg. by extending theactive ingredient with solvents and/or carriers, if desired usingemulsifiers and dispersants, it being possible also to use other organicsolvents as auxiliary solvents if water is used as the diluent. Suitableauxiliaries for this purpose are essentially: solvents such as aromatics(eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (eg.mineral oil fractions), alcohols (eg. methanol, butanol), ketones (eg.cyclohexanone), amines (eg. ethanolamine, dimethylformamide) and water;carriers such as ground natural minerals (eg. kaolins, clays, talc,chalk) and ground synthetic minerals (eg. finely divided silica,silicates); emulsifiers such as nonionic and anionic emulsifiers (eg.polyoxyethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates) and dispersants such as lignosulfite waste liquors andmethylcellulose.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, eg. ligno-,phenol-, naphthalene- and dibutylnaphthalene-sulfonic acid, and of fattyacids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fattyalcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols,or of fatty alcohol glycol ethers, condensates of sulfonated naphthaleneand its derivatives with formaldehyde, condensates of naphthalene or ofthe naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- ornonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycolethers, alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers or polyoxypropylene, lauryl alcoholpolyglycol ether acetate, sorbitol esters, lignosulfite waste liquors ormethylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixingor jointly grinding the compounds I or II and/or III to V, or themixture of the compounds I and II and/or III to V, with a solid carrier.

Granules (eg. coated granules, impregnated granules or homogeneousgranules) are usually prepared by binding the active ingredient, oractive ingredients, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths, such assilicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials, andfertilizers such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas, and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nut-shell meal, cellulose powders or othersolid carriers.

The formulations generally comprise from 0.1 to 95% by weight,preferably from 0.5 to 90% by weight, of one of the compounds I or II orof the mixture of the compounds I and II and/or III to V. The activeingredients are employed in a purity of from 90% to 100%, preferablyfrom 95% to 100% (according to NMR spectrum or HPLC).

The compounds I or II and/or III to V, the mixtures, or thecorresponding formulations, are applied by treating the harmful fungi,their habitat, or the plants, seeds, soils, areas, materials or spacesto be kept free from them with a fungicidally effective amount of themixture, or of the compounds I and II and/or III to V in the case ofseparate application.

Application can be effected before or after infection by the harmfulfungi.

Examples of such preparations comprising the active ingredients are:

I. A solution of 90 parts by weight of the active ingredients and 10parts by weight of N-methylpyrrolidone; this solution is suitable foruse in the form of microdrops;

II. A mixture of 20 parts by weight of the active ingredients, 80 partsby weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol ofethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts byweight of the calcium salt of dodecylbenzenesulfonate, 5 parts by weightof the adduct of 40 mol of ethylene oxide to 1 mol of castor oil; adispersion is obtained by finely distributing the solution in water;III. An aqueous dispersion of 20 parts by weight of the activeingredients, 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxideto 1 mol of castor oil;IV. An aqueous dispersion of 20 parts by weight of the activeingredients, 25 parts by weight of cyclohexanol, 65 parts by weight of amineral oil fraction of boiling point 210 to 280° C., and 10 parts byweight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil;V. A mixture, ground in a hammer mill, of 80 parts by weight of theactive ingredients, 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-1-sulfonate, 10 parts by weight of the sodium saltof a lignosulfonic acid from a sulfite waste liquor and 7 parts byweight of pulverulent silica gel; a spray mixture is obtained by finelydistributing the mixture in water;VI. An intimate mixture of 3 parts by weight of the active ingredientsand 97 parts by weight of finely divided kaolin; this dust comprises 3%by weight of active ingredient;VII. An intimate mixture of 30 parts by weight of the activeingredients, 92 parts by weight of pulverulent silica gel and 8 parts byweight of paraffin oil which has been sprayed onto the surface of thissilica gel; this formulation imparts good adhesion to the activeingredient;VIII. A stable aqueous dispersion of 40 parts by weight of the activeingredients, 10 parts by weight of the sodium salt of a phenolsulfonicacid/urea/formaldehyde condensate, 2 parts by weight of silica gel and48 parts by weight of water; this dispersion may be diluted further;IX. A stable oily dispersion of 20 parts by weight of the activeingredients, 2 parts by weight of the calcium salt ofdodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycolether, 20 parts by weight of the sodium salt of a phenolsulfonicacid/urea/formaldehyde condensate and 88 parts by weight of a paraffinicmineral oil.

USE EXAMPLE

The synergistic activity of the mixtures according to the invention canbe demonstrated by the following experiments:

The active ingredients, separately or together, are formulated as a 10%emulsion in a mixture of 63% by weight of cyclohexanone and 27% byweight of emulsifier, and diluted with water to the desiredconcentration.

Evaluation is carried out by determining the infected leaf areas inpercent. These percentages are converted into efficacies. The efficacy(W) is calculated as follows using Abbot's formula:W=(1−a)·100/βa corresponds to the fungal infection of the treated plants in % andβ corresponds to the fungal infection of the untreated (control) plantsin %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of the mixtures of the active ingredients aredetermined using Colby's formula [R. S. Colby, Weeds 15, 20-22 (1967)]and compared with the observed efficacies.E=x+y−x·y/100  Colby formula:E expected efficacy, expressed in % of the untreated control, when usingthe mixture of the active ingredients A and B at the concentrations aand bx efficacy, expressed in % of the untreated control, when using activeingredient A at a concentration ay efficacy, expressed in % of the untreated control, when using activeingredient B at a concentration b

Use Example 1 Activity Against Phytophthora infestans on Tomatoes

Leaves of potted plants of the variety “Groβe Fleischtomate” weresprayed to runoff point with an aqueous suspension which had beenprepared from a stock solution comprising 10% of active ingredient, 63%of cyclohexanone and 27% of emulsifier. The next day, the leaves wereinfected with an aqueous zoospore suspension of Phytophthora infestans.The plants were subsequently placed in a chamber saturated with watervapor, at temperatures between 16 and 18° C. After 6 days, the tomatoblight on the untreated but infected control plants had developed tosuch an extent that the infection could be determined visually in %.

The compounds of the formula I employed was the following compound:

The results are shown in Tables 1 and 2 below.

TABLE 1 Concentration of active ingredient Efficacy in % of in the spraythe untreated Ex. Active ingredient liquor in ppm control 1C Control 0(100% infection) 0 (untreated) 2C Compound I.1 3.1 0 4C Compound IV.33.1 0

TABLE 2 Mixtures according to the Observed Calculated Ex. invention(content in ppm) efficacy efficacy *) 5 3.1 ppm I.1 + 3.1 ppm IV.3 20 0

The test results show that the observed efficacy in all mixing ratios ishigher than the efficacy which had been calculated beforehand usingColby's formula.

We claim:
 1. A fungicidal composition comprising as active components a)an amide compound of the formula Ib

in which R⁴ is halogen and R¹¹ is phenyl which is substituted byhalogen, and d) at least one active ingredient of formulae IV.1 to IV.5,

wherein the active components are present in synergistically effectiveamounts.
 2. The composition defined in claim 1, wherein the amidecompound is a compound of formula


3. The composition defined in claim 1, which is conditioned in twoparts, one part comprising the amide compound of formula I in a solid orliquid carrier and the other part comprising one or more activeingredients of formulae IV.1 to IV.5 in a solid or liquid carrier.
 4. Amethod for controlling harmful fungi, which comprises treating thefungi, their habitat, or materials, plants, seeds, soils, areas orspaces to be protected against fungal attack with an effective amount ofthe composition defined in claim 1, wherein the active components areapplied simultaneously, that is either together or separately, or insuccession.
 5. The composition defined in claim 1, which furthercomprises 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea of formula VH₃CCH₂—NHCONH—C(CN)═NOCH₃  V.
 6. The method of claim 4, wherein thecomposition further comprises1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea of formula VH₃CCH₂—NHCONH—C(CN)═NOCH₃  V.
 7. The composition defined in claim 1,wherein the active components (a) and (d) are present in a weight ratioof from 20:1 to 1:20.
 8. The composition defined in claim 7, wherein theactive components (a) and (d) are present in a weight ratio of from 10:1to 1:10.
 9. The method of claim 4, wherein the active components (a) and(d) are applied in a weight ratio of from 20:1 to 1:20.
 10. The methodof claim 9, wherein the active components (a) and (d) are applied in aweight ratio of from 10:1 to 1:10.
 11. The method of claim 4, whereinthe composition is applied to the fungi, their habitat, or to materials,plants, soils or areas in an amount of from 0.01 to 8.0 kg/ha.
 12. Themethod of claim 4, wherein the composition is applied to seeds in anamount of from 0.001 to 250 g/kg.